Quinolyl and isoquinolyl insecticidal compounds

ABSTRACT

Insecticides of the general formula ##STR1## wherein R 1  is an optionally substituted 5- to 10-member heterocyclic moiety; R 2  is an optionally substituted alkyl, cycloalkyl or alkenyl moiety; X is oxygen, sulfur or --NH--; and R 3  is: (a) an optionally substituted 3-phenoxyphenalkyl, 3-phenoxypyridylalkyl, 3-(pyridyloxy)phenalkyl, 3-phenylaminophenalkyl, 3-benzylphenalkyl or 3-benzyloxyphenalkyl moiety; (b) a benzylfuranylmethyl moiety; (c) a 3- or 4-substituted benzyl or tetrafluorobenzyl moiety; (d) 4-phenoxy-20-butyn-2-yl; or (e) 2-methyl-3-phenylbenzyl.

This is a divisional of application Ser. No. 263,604, filed Oct. 31,1988, now U.S. Pat. No. 4,994,423 which is a continuation-in-part ofapplication Ser. No. 121,839, filed Nov. 17, 1987 now abandoned.

This invention relates to a series of insecticidal heterocycliccompounds having the general formula ##STR2## wherein R₁ is anoptionally substituted 5- to 10-member heterocyclic moiety;

R₂ is an optionally substituted alkyl, cycloalkyl or alkenyl moiety;

X is oxygen, sulfur or --NH--; and

R₃ is: (a) an optionally substituted 3-phenoxyphenalkyl,3-phenoxypyridylalkyl, 3-(pyridyloxy)phenalkyl, 3-phenylaminophenalkyl,3-benzylphenalkyl or 3-benzyloxyphenalkyl moiety; (b) abenzylfuranylmethyl moiety; (c) a 3- or 4-substituted benzyl ortetrafluorobenzyl moiety; (d) 4-phenoxy-2-butyn-2-yl; or (e)2-methyl-3-phenylbenzyl.

More specifically, R₁ is a heterocyclic moiety selected from pyridyl,quinolyl, isoquinolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,thiadiazolyl, furanyl, pyrazolyl, or benzoxazolyl or benzothiazolylbonded to the imidate/amidine nitrogen atom through an aromatic carbonatom, said heterocyclic moiety being optionally substituted by from 1 to4 groups selected from halo, C₁ -C₆ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄haloalkoxy, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, methoxycarbonyl, or phenyl,provided that R₁ is not 3-chloro-5-trifluoromethyl-pyrid-2-yl;

R₂ is methyl, ethyl, n-propyl, C₃ -C₇ branched alkyl, C₃ -C₄ cycloalkyl,C₂ -C₆ alkenyl, C₂ -C₆ haloalkenyl, C₁ -C₆ haloalkyl, C₂ -C₆ alkoxyalkylor cyclopropyl substituted by up to four methyl groups or up to twohalogens;

X is oxygen, sulfur or --NH--;

when X is oxygen, then R₃ is:

(a) ##STR3## in which m is 0 or 1; A, B and C are each carbon ornitrogen, provided that A, B and C are not all nitrogen and if two of A,B and C are nitrogen, then A and C are nitrogen;

R₄ is hydrogen, monohalo or dihalo;

R₆ is hydrogen, methyl, fluoro or ethynyl; and

R₇ is

(i) ##STR4## in which D and E are each carbon or nitrogen provided thatboth D and E are not nitrogen, and further provided that if any of A, Bor C is nitrogen, then D and E are both carbon; and

R₅ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethyl, cyano, C₁-C₄ alkylthio, C₁ -C₄ alkylsulfonyl, or mono- or polyhalo;

(ii) ##STR5## in which R₈ is hydrogen or halogen; or (iii) --O--CH₂--CH═CH₂ ;

(b) ##STR6## in which (i) R₉ is 4-fluoro, 4-methoxymethyl, or4-propargyl, and R₁₀ is fluoro or

(ii) R₉ is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(mono- ordihalo)allyl, and R₁₀ is hydrogen or fluoro;

(c) ##STR7## (d) 4-phenoxy-2-butyn-2-yl; (e) 3-bromo-4-fluorobenzyl;

(f) 4-(benzyloxy)benzyl;

(g) 4-(4-fluorobenzyloxy)benzyl; or

(h) ##STR8## and when X is sulfur or --NH--, then R₃ is

(j) ##STR9## in which n is 0 or 1; F and G are independently nitrogen orcarbon, provided that F and G are not both nitrogen; R₁₁ is hydrogen orhalo; R₁₂ is hydrogen, mono- or di-halo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,trifluoromethyl, cyano, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl; and R₁₃is hydrogen or methyl; (k) pentafluorobenzyl; or (1)2-methyl-3-phenylbenzyl.

The compounds of this invention demonstrate activity in controllingvarious types of insects, particularly in foliar application.

Another aspect of this invention involves insecticidal compositioncomprising an insecticidally effective amount of a compound of theinvention with an insecticidally suitable diluent or carrier.

In another aspect, this invention involves a method for controllinginsects by administration of insecticidally effective amounts of thecompounds of compositions of this invention to a locus where control isdesired.

The term "insects" as used herein refers to the broad and commonlyunderstood usage rather than to those creatures which in the strictbiological sense are classified as insects. In addition to thosebelonging to the class Insecta, this term may include some classes ofacarids such as mites and the like.

DETAILED DESCRIPTION OF THE INVENTION

The novel compounds of this invention have the general formula ##STR10##in which R₁, R₂, R₃ and X are as defined above. The term"imidate/amidine nitrogen atom" will be used to refer to the nitrogenatom shown in this general formula.

As used herein:

"halo" includes chloro, bromo, fluoro and iodo;

"alkyl" refers to saturated acyclic hydrocarbyl groups (straight orbranched chain) having the indicated number of carbon atoms, e.g.,methyl, ethyl, n-propyl, isopropyl, etc.;

"haloalkyl" and "haloalkoxy" refer to alkyl and alkoxy groups of theindicated number of carbon atoms substituted by one or more of the sameor different halogen atoms;

"cycloalkyl" refers to saturated cyclic hydrocarbyl groups having theindicated number of carbon atoms, e.g., cyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl;

"alkenyl" refers to unsaturated acyclic hydrocarbyl groups having theindicated number of carbon atoms and including one or more olefinicbonds, e.g., vinyl, propenyl, isopropenyl, 1-butenyl, butadienyl, andthe like; and

"alkoxyalkyl" refers to saturated acyclic moieties having two alkylgroups linked by an oxygen atom, with the total number of carbon atomsindicated, e.g., methoxymethyl, methoxyethyl, ethoxymethyl and the like;

"phenalkyl" refers to an alkyl group having from 1 to 4 carbon atomssubstituted by a phenyl group, such as benzyl, phenethyl, and the like;

"propargyl" refers to the 2-propynyl group, --CH2--C.tbd.CH, and

"allyl" refers to the 2-propenyl group --CH2--CH═CH2.

In general, R₁ is a 5- to 10-member heterocyclic moiety, containing 1 or2 rings, optionally substituted as described below. The heterocyclicgroups represented by R₁, except for benzoxazolyl and benzothiazolyl,may be bonded to the imidate/amidine nitrogen atom at any position onthe ring. The pyridyl groups thus include 2-, 3- and 4-pyridyl, Thebenzoxazolyl and benzothiazolyl groups have the formula ##STR11## inwhich Y is oxygen or sulfur, respectively. In the compounds of thisinvention, these moieties are bonded to the imidate/amidine nitrogenatom through a carbon atom in the "aromatic" portion of the ring, thatis, at the 4-, 5-, 6- or 7-position.

The heterocyclic ring represented by R₁ may be unsubstituted or may besubstituted at any position by one or more halo, alkyl, alkoxy,haloalkyl, alkylthio, haloalkoxy, alkylsulfonyl, carbomethoxy, or phenylgroups, or by a combination of such groups. Preferred substituted ringsinclude:

mono- and disubstituted pyridyl in which the substituents are halo,trifluoromethyl, methoxy, ethoxy, 2,2,2-trifluoroethoxy, methylthio,and/or methyl, except 3-chloro-5-trifluoromethyl-pyrid-2-yl;

mono-substituted oxazolyl, thiazolyl and thiadiazolyl rings in which thesubstituent is halo, methyl or trifluoromethyl; and

2-(C₁ -C₄ alkyl) benzoxazolyl and benzothiazolyl.

For the various subgroups falling within the general definition of R₃,preferred types are:

For R₄ and R₁₂ : hydrogen and 2-,4- or 6-monohalo, particularlymonochloro or monofluoro;

For R₅ and R₁₃ : 2-, 3- or 4-halo, 2,4-, 3,4- or 3,5-dihalo,particularly difluoro, pentahalo, particularly pentafluoro, 4-methyl,4-trifluoromethyl, 4-methoxy, 4-methylthio and 4-methylsulfonyl.

The following are examples of specific embodiments of groups fallingwithin the definition of R₃. For convenience in specifying positions ofsubstitution of compounds of the type ##STR12## the position ofattachment of the group ##STR13## was given the number 1 and theposition of attachment of group R₇, the number 3. When A, B or C was anitrogen atom, the compounds were designated pyrid-2-yl, pyrid-6-yl, orpyrid-4-yl, respectively.

3-phenoxybenzyl,

3-phenoxy-(alpha-methyl)benzyl,

3-phenoxyphenethyl,

3-(4-pyridyloxy)benzyl,

4-pyridyloxybenzyl,

3-(4-fluorophenoxy)benzyl,

3-(4-chlorophenoxy)benzyl,

3-(4-bromophenoxy)benzyl,

3-(4-iodophenoxy)benzyl,

3-(2,4-difluorophenoxy)benzyl,

3-(3,4-difluorophenoxy)benzyl,

3-(3,5-difluorophenoxy)benzyl,

3-(2,3,4,5,6-pentafluorophenoxy)benzyl,

3-(4-fluorophenoxy)-4-fluorobenzyl,

3-(4-fluorophenoxy)-4-chlorobenzyl,

3-(4-chlorophenoxy)-4-fluorobenzyl,

3-phenoxy-4-fluorobenzyl,

3-(4-fluorophenoxy)-6-chlorobenzyl,

3-(4-fluorophenoxy)-5-fluorobenzyl,

3-(4-fluorophenoxy)-4,6-difluorobenzyl,

3-(4-methylphenoxy)benzyl,

3-(4-methoxyphenoxy)benzyl,

3-(3,4-difluorophenoxy)-4-fluorobenzyl,

3-(3-fluorophenoxy)benzyl,

3-(2-fluorophenoxy)benzyl,

3-(3-chlorophenoxy)benzyl,

3-(4-trifluoromethylphenoxy)benzyl,

3-(4-methylthiophenoxy)benzyl,

3-(4-fluorophenoxy)-(alpha-fluoro)benzyl,

3-phenoxy-pyrid-2-yl methyl,

3-phenoxy-pyrid-4-yl methyl,

3-phenoxy-pyrid-6-yl methyl,

3-(4-methylphenoxy)pyrid-2-ylmethyl,

3-(4-fluorophenoxy)pyrid-2-ylmethyl,

3-(4-chlorophenoxy)pyrid-2-ylmethyl,

3-(4-fluorophenoxy)pyrid-4-ylmethyl,

3-(4-bromophenoxy)pyrid-2-ylmethyl,

3-(4-chlorophenoxy)pyrid-4-ylmethyl,

3-(4-chlorophenoxy)pyrid-6-ylmethyl,

3-(3,4-difluorophenoxy)pyrid-2-ylmethyl,

3-(pyrid-2-yloxy)benzyl,

3-(4-chloropyrid-2-yloxy)benzyl,

2,3,4,5,6-tetrafluorobenzyl,

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl,

4-propargyl-2,3,5,6-tetrafluorobenzyl,

3-allyloxybenzyl,

1-3-phenoxyphenyl)prop-2-ynyl,

3-(benzyl)benzyl,

3-(benzyloxy)benzyl,

3-(4-fluorobenzyloxy)benzyl,

3-(phenylamino)benzyl,

3-(4-fluorophenylamino)benzyl,

2-methyl-3-phenylbenzyl,

3-bromo-4-fluorobenzyl,

4-phenoxy-2-butyn-2-yl,

4-(4-fluorobenzyloxy)benzyl,

5-benzyl-3-furanylmethyl.

The compounds of this invention may be prepared by the followingprocesses in which R₁, R₂, R₃ and X are as previously defined.

Products of type (I) in which X is oxygen are prepared by reaction of animidoyl chloride with an alkali metal alkoxide according to the generalreaction (A) ##STR14## in which M is an alkali metal, preferably sodiumor potassium.

This reaction is conducted at a temperature of from about -70° C. toabout +65° C., most preferably at about room temperature, for a timewhich may range from about 5 minutes up to about 48 hours. The reactionis conducted in the presence of a solvent, for example, an aromatichydrocarbon such as benzene, toluene, xylene or naphthalene, or anether, such as diethyl ether, diisopropyl ether, diisoamyl ether,dibutyl ether, furan, 1,2-dimethoxyethane, or tetrahydrofuran(preferably tetrahydrofuran). In some instances, apparent to thoseskilled in the art, it is advantageous to add the solution of the alkalimetal alkoxide to a solution of the imidoyl chloride or to usesubstantial excesses of alkoxide. The resulting product may be recoveredby conventional techniques.

The alkoxide R₃ OM is produced by reaction of an appropriate alcohol,such as 3-phenoxybenzyl alcohol, with an alkali metal-containing base,for instance, an alkali metal hydride (e.g., potassium or preferablysodium hydride) in the presence of a solvent such as that used inreaction of the alkali metal alkoxide with the imidoyl chloride. Ingeneral, this reaction is conducted at reflux temperature under an inertatmosphere for a time which may range up to about 2 hours.

Some compounds of this invention are produced from alcohols (R₃ OH)which are sensitive to, and could be adversely affected (e.g.decomposed) by, strong bases such as the alkali metal-containing bases(e.g. alkali metal hydrides) used to prepare the alkoxides (R₃ OM).Alcohols which may be sensitive to such strong bases includephenoxypyridyl alkanols, alpha-ethynyl alcohols (R₆ is ethynyl) such as1-(3-phenoxyphenyl)-2-propyn-1-ol and tetrafluoropropargylbenzylalcohol.

Compounds of this type may be made by direct reaction of the alcoholwith the imidoyl chloride in the presence of a tertiary amine base and areaction-promoting amount of a 4-(di-lower alkyl)aminopyridine,preferably 4-dimethylaminopyridine.

Tertiary amines which may be used in this process include trialkylaminessuch as trimethyl-, triethyl-, tri-n-butyl-amine and the like, includingtertiary amines having mixed alkyl groups, N,N-dialkylanilines such asN,N-dimethylaniline, pyridine and various substituted pyridines.

Preferred tertiary amines, primarily for economic reasons, aretriethylamine, N,N-diemthylaniline, and pyridine. The tertiary amine mayeven be an additional amount of the promoter 4(di-loweralkyl)aminopyridine, over and above that amount needed for promoting thereaction.

The tertiary amine is preferably used in a stoichiometric amount withrespect to the alcohol, but may be used in excess of that amount. Thepromoter 4-(di-lower alkyl)aminopyridine may be used in an amount fromabout 0.05 to about 1 equivalent per equivalent of alcohol, preferablyfrom about 0.05 to about 0.15 equivalent per equivalent, most preferablyabout 0.1.

This process is preferably conducted at temperatures of from about 20°C. to about 50° C. Lower temperatures may be used, but the reaction ratewould be much slower. The process is carried out in the presence of aninert solvent such as an aromatic hydrocarbon (for instance, benzene,toluene or xylene), a chlorinated solvent (such as methylene chloride,ethylene dichloride or chlorobenzene) or an ether (such as diethylether, dioxane or tetrahydrofuran).

While this process is particularly suitable for producing compounds frombase-sensitive alcohols, it may be used to produce compounds of thisinvention in general from other alcohols as described.

The alcohols, if not commercially available, can be prepared accordingto known methods such as those described in U.S. Pat. Nos. 4,256,893;4,261,920 and 4,329,518, as Volumn 7 of the text "Chemie derPflanzenschutz und Schadlingsbekampfungsmittel" (for phenoxybenzyl,phenoxypyridyl and pyridyloxybenzyl type alcohols); in the article byElliott et al. J. Chem. Soc. (C), 1971, pp 2551-2554 (forS-benzyl-2-furanylmethanol); Pesticide Science 14, 560-570 (1983) (for2-methyl-3-phenylbenzyl alcohol); U.S. Pat. Nos. 4,370,346 and4,594,355; British patent 2,122,616; European patent applications196,156 and 271,240; and J. Sci. Food & Agriculture 18, 167 (1967) forvarious substituted benzyl alcohols; European patent application 211,561for 3-phenylaminobenzyl alcohols; Swiss patent 549,342 for4-phenoxy-2-butyl-1-ol; and Japanese patent 49-27331 for1-(3-phenoxyphenyl)-2-propyn-1-ol.

Alpha-fluorophenoxybenzyl compounds are made from the alpha-fluorobenzylhalide (preferably bromide) rather than the alcohol by reaction with anamide R₁ NHCOR₂ in the presence of a halide ion binding agent such assilver oxide or a silver salt and an inert solvent. Reactiontemperatures are from about -20° C. to about 100° C.

The imidoyl chloride may be prepared from a starting amine having theformula R₁ NH₂ or amide having the formula ##STR15## depending onavailability. The amines are either generally available or may beprepared by procedures known in the art, for example, those described in"Compendium or Organic Synthetic Methods", Harrison et al.(Wiley-Interscience, New York, 1971).

The amides, if not available, may be produced by reaction of the aminewith an appropriate acid chloride having the formula ##STR16## Thetemperature of this reaction ranges from about -40° C. to about +80° C.Suitable solvents include hydrocarbon solvents such as toluene andchlorinated hydrocarbon solvents such as methylene chloride, chloroform,carbon tetrachloride, ethylene dichloride, tetrachloroethane and thelike, preferably methylene chloride. This reaction is conducted in thepresence of a base, preferably a tertiary amine. Suitable bases includetriethylamine, quinoline, diemthylaniline, and pyridine. Triethylamineis the preferred base. The resulting amide is recovered and purified byconventional means.

The imidoyl chloride may be prepared from the amide by reacting it witha chlorinating agent such as phosphorus pentachloride or phosgene in anorganic solvent such as that utilized in the amide production(preferably methylene chloride). The reaction is carried out under aninert atmosphere for a time which may range up to 10 hours, preferablyfrom 1 to 4 hours, at a temperature of from about 0° C. to about 110° C.

Before the imidoyl chloride-containing product is passed to the finalstep, all substances, such as phosphorus oxychloride or hydrogenchloride, which can react with the alkoxide, mercaptide, mercaptan oramine in the final step, should be removed. This can generally beaccomplished by evaporation or distillation.

Compounds in which X is sulfur may be prepared similarly to those inwhich X is oxygen (by formation of the alkali metal mercaptide).Alternatively, they may be prepared by reaction of the correspondingimidoyl chloride with the appropriate mercaptan in the presence of abase according to the reaction ##STR17##

This process is carried out under reflux for a time of between about 30and about 60 minutes. The base utilized is a tertiary amine such as thatemployed for production of the amide from the amine and is preferablytriethylamine. This reaction is conducted in the presence of a suitablesolvent such as that utilized in the reaction of an alkali metalalkoxide with the imidoyl chloride, and is preferably tetrahydrofuran.The reaction between the mercaptan and the imidoyl chloride isexothermic; consequently the addition of imidoyl chloride should becarefully controlled. The product may be recovered by conventionaltechniques.

Mercaptans of the formula R₃ SH are described in German PatentApplication 2,944,849.

Compounds in which X is sulfur may also be prepared by alkylation of athioamide according to the reaction: ##STR18## in which R₁, R₂ and R₃are as defined above, and Hal stands for halo preferably chloro.

The thioamides, if not readily available, may be produced by reaction ofthe corresponding amine and Lawesson's Reagent. Reaction (C) isgenerally conducted at a temperature of from about -20° to about 110°C., for a time of from about 1 to about 20 hours, in the presence of asolvent, for instance an aromatic hydrocarbon such as benzene, toluene,xylene or naphthalene or an ether such as diethyl, diisopropyl,diisoamyl or dibutyl ether, furan, tetrahydrofuran, or1,2-dimethoxyethane, and an appropriate base such as an alkali metalhydride. The final product may be recovered by conventional techniques.

Compounds in which X is nitrogen may be produced by reaction of theappropriate imidoyl chloride with an amine according to the reaction##STR19## Again, a suitable solvent is tetrahydrofuran. This reactionmay take up to 48 hours to complete and is conducted under an inertatmosphere at temperatures of -40° to +80° C. Again, the imidoylchloride should be added in a controlled manner in order to maintain thetemperature within the appropriate range. The starting amines aredescribed for instance in European Patent Applications 6155 and 6180.The base is a tertiary amine, preferably triethylamine. The resultingproduct is recovered by conventional techniques.

The following represents an example of the preparation of compounds ofthis invention.

EXAMPLE

This example illustrate the general procedure for the preparation ofcompounds of this invention according to Reaction (A).

Preparation ofN-(6-Chloro-3-pyridyl)-O-(3-phenoxybenzyl)isobutyrylimidate (Compound 1)A. Preparation of the Amide

To a stirred solution of 10 grams (g) (0.078 mol)5-amino-2-chloropyridine, and triethylamine (11.2 ml, 0.08 mol) in 100ml of dichloromethane was added to 7.8 ml (0.075 mol) of isobutyrylchloride dropwise chloromethane was added 7.8 ml (0.075 mol) ofisobutyryl chloride dropwise with cooling in an ice bath. Following theaddition, the ice bath was removed and when the reaction mixture reachedroom temperature, 100 ml of water was added. The layers were separatedand the organic layer was dried over anhydrous sodium sulfate. Rotaryevaporation provided 6-chloro-3-pyridylisobutyrylamide. The crude solidcould be recrystallized from toluene to provide crystals, m.p. 118°-120°C.

B. Preparation of the Imidoyl Chloride

To a stirred solution of the product of step (A) (2.0 g, 0.010 mol) in50 ml of dichloromethane under an argon atmosphere was addedphosphosphorus pentachloride (2.1 g, 0.010 mol). After 2 hours, theresulting solution was transferred to a rotary evaporator. The solventwas removed at 20 mmHg and the residue was evaporated at 40° under avacuum of less than 1 mm Hg. The resultantN-(6-chloro-3-pyridyl)-1-chloro-2-methylpropylidene amine as a viscousoil, was immediately carried on to Step D.

C. Preparation of the Alkoxide

To a stirred suspension of sodium hydride (0.29 g, 0.012 mol) in 40 mlof dry tetrahydrofuran (THF) under argon was added 2.2 g (0.011 mol) of3-phenoxybenzyl alcohol. The resulting mixture was heated to reflux for30 minutes and cooled. The resulting pale yellow solution of sodium3-phenoxybenzylate was used in the final Step D.

D. Preparation of the Imidate

Crude imidoyl chloride from step (B) was dissolved in 10 ml of dry THFand added dropwise to the THF solution of alkoxide from step (C) withcooling at room temperature for several minutes. After an additionalhour, the resulting product mixture was poured into hexane. It was thenfiltered through a pad of 25 g of silica gel. Rotary evaporationresulted in 2.9 g (76%) of a white solid, shown to beN-(6-chloro-3-pyridyl)-O-(3-phenoxybenzyl)isobutyrylimidate (I), m.p.69°-77° C.

Table I shows representative compounds of this invention preparedaccording to the procedures described above.

                                      TABLE I                                     __________________________________________________________________________     ##STR20##                                                                                                                           Physical               Cmpd. No.                                                                           X   R.sub.1         R.sub.2  R.sub.3             Constant               __________________________________________________________________________     1    O                                                                                  ##STR21##      isopropyl                                                                              3-phenoxybenzyl     m.p. 69-77°                                                            C.                      2    O                                                                                  ##STR22##      isopropyl                                                                              3-phenoxybenzyl     oil                     3    O                                                                                  ##STR23##      isopropyl                                                                              3-phenoxybenzyl     oil                     4    O                                                                                  ##STR24##      isopropyl                                                                              3-phenoxybenzyl     m.p. 50-55°                                                            C.                      5    O                                                                                  ##STR25##      isopropyl                                                                              3-phenoxybenzyl     oil                     6    O                                                                                  ##STR26##      isopropyl                                                                              3-phenoxybenzyl     oil                     7    O                                                                                  ##STR27##                                                                                     ##STR28##                                                                             3-phenoxybenzyl     oil                     8    O                                                                                  ##STR29##      isopropyl                                                                              3-phenoxybenzyl     oil                     9    O                                                                                  ##STR30##                                                                                     ##STR31##                                                                             3-phenoxybenzyl     oil                    10    O                                                                                  ##STR32##      isopropyl                                                                              3-phenoxybenzyl     oil                    11    O                                                                                  ##STR33##      isopropyl                                                                              3-phenoxybenzyl     oil                    12    O                                                                                  ##STR34##                                                                                     ##STR35##                                                                             3-phenoxybenzyl     oil                    13    O                                                                                  ##STR36##      isopropyl                                                                              3-phenoxybenzyl     oil                    14    O                                                                                  ##STR37##      isopropyl                                                                              3-phenoxybenzyl     oil                    15    O                                                                                  ##STR38##                                                                                     ##STR39##                                                                             3-phenoxybenzyl     oil                    16    O                                                                                  ##STR40##      isopropyl                                                                              3-phenoxybenzyl     oil                    17    O                                                                                  ##STR41##      isopropyl                                                                              3-phenoxybenzyl     oil                    18    O                                                                                  ##STR42##      isopropyl                                                                              3-phenoxybenzyl     oil                    19    O                                                                                  ##STR43##      isopropyl                                                                              3-phenoxybenzyl     oil                    20    O                                                                                  ##STR44##      isopropyl                                                                              3-phenoxybenzyl     oil                    21    O                                                                                  ##STR45##      isopropyl                                                                              3-phenoxybenzyl     oil                    22    O                                                                                  ##STR46##      isopropyl                                                                               ##STR47##          oil                    23    NH                                                                                 ##STR48##      isopropyl                                                                              3-phenoxybenzyl     oil                    24    O                                                                                  ##STR49##      isopropyl                                                                              3-phenoxybenzyl     oil                    25    O                                                                                  ##STR50##      isopropyl                                                                              3-phenoxybenzyl     oil                    26    O                                                                                  ##STR51##      isopropyl                                                                              3-phenoxybenzyl     oil                    27    O                                                                                  ##STR52##      isopropyl                                                                              3-phenoxybenzyl     oil                    28    O                                                                                  ##STR53##      isopropyl                                                                              3-phenoxybenzyl     oil                    29    S                                                                                  ##STR54##      isopropyl                                                                               ##STR55##          oil                    30    O                                                                                  ##STR56##      isopropyl                                                                               ##STR57##          oil                    31    O                                                                                  ##STR58##      isopropyl                                                                               ##STR59##          oil                    32    O                                                                                  ##STR60##      isopropyl                                                                               ##STR61##          oil                    33    O                                                                                  ##STR62##      isopropyl                                                                              3-phenoxybenzyl     oil                    34    O                                                                                  ##STR63##      isopropyl                                                                              3-phenoxybenzyl     oil                    35    O                                                                                  ##STR64##      isopropyl                                                                               ##STR65##          oil                    36    O                                                                                  ##STR66##      isopropyl                                                                               ##STR67##          oil                    37    O                                                                                  ##STR68##      isopropyl                                                                               ##STR69##          oil                    38    O                                                                                  ##STR70##      isopropyl                                                                              3-phenoxybenzyl     oil                    39    O                                                                                  ##STR71##      isopropyl                                                                               ##STR72##          oil                    40    O                                                                                  ##STR73##      isopropyl                                                                              3-phenoxybenzyl                            41    O                                                                                  ##STR74##      isopropyl                                                                              3-phenoxybenzyl     oil                    42    O                                                                                  ##STR75##      isopropyl                                                                               ##STR76##          oil                    43    O                                                                                  ##STR77##      isopropyl                                                                               ##STR78##          oil                    44    O                                                                                  ##STR79##      isopropyl                                                                               ##STR80##          oil                    45    O                                                                                  ##STR81##      isopropyl                                                                               ##STR82##          oil                    46    O                                                                                  ##STR83##      isopropyl                                                                               ##STR84##          oil                    47    O                                                                                  ##STR85##      C(CH.sub.3)CH.sub.2                                                                    3-phenoxybenzyl     oil                    48    O                                                                                  ##STR86##      C(CH.sub.3)CH.sub.2                                                                     ##STR87##          oil                    49    O                                                                                  ##STR88##      C(CH.sub.3)CH.sub.2                                                                     ##STR89##          oil                    __________________________________________________________________________

INSECTICIDAL EVALUATION TESTS

The compounds in Table I above were tested for insecticidal activityusing the following testing procedures. LC₅₀ values, based on theresults of these tests and calculated according to dosage-mortalitycurves, are expressed in Table II.

Housefly [Musca domestica]

The test compound was diluted in acetone and aliquots pipetted onto thebottom of aluminum dishes. To ensure even spreading of the chemical onthe bottom of the dishes, 1 ml of acetone containing 0.01% peanut oilwas also added to each dish. After all solvents had evaporated, thedishes were placed in circular cardboard cages containing 25 femalehouseflies, 1-2 days old. The cages were covered on the bottom withcellophane and on the top with tulle netting, and each contained asugar-water saturated cotton plug for maintenance of the flies.Mortality was recorded after 48 hours. Test levels ranged from 100 μg/25female houseflies downward. The LC-50 value is expressed below in TableII under the heading "HF", in terms of μg of the test compound per 25female flies.

Black Bean Aphid [Aphis fabae (Scop.)]

Nasturtium plants (Tropaeolum sp.) approximately 5 cm tall, weretransplanted into sandy loam soil in small cups and infested with 25-50black bean aphids of mixed ages. Twenty-four hours later they weresprayed to the point of runoff with 50-50 acetone-water solutions of thetest compound. Treated plants were held in the greenhouse and mortalitywas recorded after 48 hours. Test concentrations ranged from 0.05%downward. The LC-50 value is expressed below in Table II under theheading "BA" in terms of percent of the test compound in the sprayedsolution.

Tobacco Budworm [Heliothis virescens (Fabricius)]

Eggs: Paper towel patches of 2-day old eggs of the tobacco budworm weredipped in acetone solutions of the test compound and placed in petridishes containing a portion of larval rearing medium. Treated eggs weremaintained at 78° F. and mortality was recorded after all control eggshad hatches and the young larvae were feeding on the media. Testconcentrations ranged from 0.1% downward. The LC-50 value is expressedbelow in Table II under the heading "TBW-E" in terms of percent of thetest compound in the solution.

Cabbage Looper [Trichlplusia ni (Hubner)]

The test compound was diluted in a 50-50 acetone-water solution.Cotyledons of hyzini squash (Calabacita abobrinha), approximately 1×1.5inches, were immersed in the test solutions for 2-3 seconds and placedon a wire screen to dry. The dried leaves were placed in petri dishescontaining a moistened piece of filter paper and infested with 5second-instar cabbage looper larvae. The dishes were placed in a highhumidity chamber. Mortality of the larvae was recorded 3-5 days later.Test concentrations ranged from 0.1% downward. The LC-50 value isexpressed below in Table II under the heading "CL" in terms of percentof the test compound in solution.

Western Spotted Cucumber Beetle Larvae [Diabrotica undecimpunctataundecimpunctate (Mannherheim)]

Ten grams of moist potting soil was placed in a plastic cup. The testcompound was dissolved in acetone. A 0.05 ml aliquot of the test sample,diluted to the desired concentration, was added to the soil. The cup wascapped and the soil was mixed on a vortex mixer for approximately 15seconds. An indentation was made on the surface of the soil andapproximately 50 Diabrotica eggs were added. The eggs were covered withsoil and maintained at room temperature (approximately 70° F. or 21°C.). Four days later a section of Romaine lettuce (Latuca sativa) leafwas placed in the treated cups. One week later the cups were examinedfor live larvae. Test concentrations ranged from 25 ppm downward. TheLC-50 value is expressed below in Table II under the heading"Diabrotica" in terms of ppm of the test compound in the soil.

ACARICIDAL EVALUATION TEST

The two-spotted mite (2SM) [Tetranychus urticae (Koch)] was employed intests for miticides. The test procedure was as follows:

Pinto bean plants (Phaseolus sp.) approximately 10 cm tall, weretransplanted into sandy loam soil in small cups and thoroughly infestedwith two-spotted mites of mixed ages and sexes. Twenty-four hours laterthe infested plants were inverted and dipped for 2-3 seconds in 50-50acetone-water solutions of the test compound. Treated plants were heldin the greenhouse, and 5-7 days layer mortality was determined for bothadult mites and the nymphs hatching from eggs which were on the plantsat the time of treatment. Test concentrations ranged from 0.05%downward. The LC-50 value is expressed below in Table II under theheadings "2SM-A" (i.e., adults) and "2SM-E" (i.e. eggs) in terms ofpercent concentration of the test compound in the solution.

The results of these tests are shown in Table II.

                                      TABLE II                                    __________________________________________________________________________    (LC.sub.50)                                                                   Cmpd.                                                                             HF    BA   2-SM    TBW CL,    Diabrotica,                                 No. ug    %    A/% E/% E/% %      ppm (soil)                                  __________________________________________________________________________     1  5.5   0.001                                                                              >0.05                                                                             >0.05                                                                             0.04                                                                              0.005  >25                                          2  18    0.003                                                                              >0.05                                                                             >0.05                                                                             0.075                                                                             0.0027 >25                                          3  7     0.003                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.0075 >25                                          4  42    0.05 >0.05                                                                             >0.05                                                                             >0.1                                                                              0.008  >25                                          5  8     0.003                                                                              >0.05                                                                             >0.05                                                                             0.09                                                                              0.008  >25                                          6  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.004  >25                                          7  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.022  >25                                          8  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.1    >25                                          9  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.035  >25                                         10  25    0.05 >0.05                                                                             >0.05                                                                             >0.1                                                                              >0.1   --                                          11  7     0.01 >0.05                                                                             >0.05                                                                             >0.1                                                                              0.01   --                                          12  12    0.05 >0.05                                                                             > 0.05                                                                            >0.1                                                                              0.02   --                                          13  7     >0.05                                                                              --  --  >0.1                                                                              0.015  --                                          14  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.01   >25                                         15  58    >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.05   >25                                         16  59    --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.025  >25                                         17  36    --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.05   >25                                         18  8     --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.009  >25                                         19  10    --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.04   >25                                         20  6     --   --  --  --  0.009  --                                          21  >100  --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.05   >25                                         22  9     --   >0.05                                                                             >0.05                                                                             0.05                                                                              0.001  >25                                         23  >100  --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.1    >25                                         24  >100  --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.0075 >25                                         25  38    --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.0075 >25                                         26  >100  0.05 >0.05                                                                             >0.05                                                                             >0.1                                                                              0.004  --                                          27  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.0035 --                                          28  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.04   >25                                         29  >100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.025  >25                                         30  15    >0.05                                                                              >0.05                                                                             >0.05                                                                             0.1 0.0007 >25                                         31  7.5   --   >0.05                                                                             >0.05                                                                             0.45                                                                              0.0016 >25                                         32  22    --   >0.05                                                                             0.05                                                                              0.03                                                                              0.00075                                                                              >25                                         33  5     >0.05                                                                              >0.05                                                                             >0.05                                                                             0.075                                                                             0.0035 >25                                         34  >100  --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.018  >25                                         35  23    --   >0.05                                                                             >0.05                                                                             0.1 0.001  >25                                         36  >100  --   >0.05                                                                             >0.05                                                                             >0.1                                                                              0.015  >25                                         37  40    >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              >0.1   >25                                         38  <100  0.005                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              >0.1   >25                                         39  >100  0.001                                                                              0.006                                                                             0.006                                                                             0.02                                                                              >0.1   >25                                         40  <100  0.0003                                                                             0.006                                                                             0.006                                                                             0.045                                                                             0.00029                                                                              >25                                         41  <100  >0.05                                                                              >0.05                                                                             >0.05                                                                             >0.1                                                                              0.0014 >25                                         42  <100  0.0004                                                                             0.006                                                                             0.006                                                                             0.017                                                                             0.000075                                                                             >25                                         43  >100  0.0003                                                                             0.006                                                                             0.006                                                                             0.02                                                                              0.00015                                                                              >25                                         44  >100  0.0003                                                                             0.001                                                                             0.001                                                                             0.01                                                                              0.00017                                                                              >25                                         45  <100  0.001                                                                              0.03                                                                              0.03                                                                              >0.1                                                                              0.00075                                                                              >25                                         46  <100  0.0003                                                                             0.006                                                                             0.006                                                                             0.017                                                                             0.00027                                                                              >25                                         47  <100  0.05 >0.05                                                                             >0.05                                                                             <0.1                                                                              <0.1   >25                                         48  <100  <0.05                                                                              >0.05                                                                             >0.05                                                                             <0.1                                                                              <0.1   >25                                         49  <100  <0.05                                                                              >0.05                                                                             >0.05                                                                             0.1 <0.1   >25                                         __________________________________________________________________________     Key:                                                                          C = Contact Test                                                              E = Test on eggs                                                              A = Test on Adults                                                       

Some compounds of this invention were also evaluated against otherinsects, including aster leafhopper (Macrosteles fascifrens [Stal]) andmaize weevil (Sitophilus zeamais [Motschulsky]). With a few exceptions,the tested compounds did not produce 50% or greater activity at thelevels tested.

The insecticidal activity of compounds defined by Formula (I) may bedetermined by evaluating such a compound using one or more of theabove-described procedures. Compounds demonstrating activity against oneor more of such insects are considered "insecticidal" for the purposesof this invention.

In practice, a pure compound (active compound) can be used as aninsecticide. However, in general, the compounds are first formulatedwith one or more inert (i.e. non-chemically reactive, plant compatibleor herbicidally inert) carriers or diluents suitable for insecticidaluse, before being applied.

The compositions or formulations, including a compound (I) as describedherein, may take any one of a number of solid or liquid forms. Examplesof solid forms are dusts, granules, tablets, powders and the like.Examples of liquid forms are emulsions, solution, suspensions,flowables, emulsifiable concentrates and pastes. Such compositions maycontain, in addition to the active compound or compounds, variouscarriers or diluents; surface-active agents (wetting agents, dispersingagents and/or emulsifying agents); solvents (water, or organic solventssuch as aromatic solvents or chlorinated aliphatic solvents); adhesives;thickeners; binders; anti-foaming agents; and other substances asmentioned herein. Solid carriers or diluents included in suchcompositions or formulations may include, for example, ground naturalminerals such as kaolins, alumina, calcined diatomaceous earth, calciumcarbonate, silica, kieselguhr, clays, etc.; ground synthetic mineralssuch as various silicates and alumino-silicates and ground vegetableproducts such as bark, cornmeal, sawdust, cellulose powder and the like.Compositions containing sorptive clays will usually also contain astabilizer, such as a glycol, to prevent or minimize degradation of theactive ingredient.

To manufacture solid compositions, the active compounds are mixed withsolid carriers or diluents such as those mentioned above and the mixtureis ground to the appropriate size. Granules can be manufactured bydissolving an active compound in an organic solvent and applying themixture, for example, by atomization, onto an absorptive granulatedinert material, such as silica. Adhesives may be utilized to assist inthe incorporation of the compound onto the solid particles.

Wettable powders and pastes are obtained by mixing and grinding anactive compound with one or more dispersing agents and/or solid carriersor diluents. Also included may be wetting agents and/or dispersingagents, for example, lignins, methyl cellulose, naphthalenesulfonic acidderivatives, fatty alcohol sulfates and various types of alkali andalkaline earth metal salts of fatty acids.

Emulsifiable concentrates are generally obtained by dissolving theactive compound in an organic solvent, for example, butanol,cyclohexanone, xylenes, or higher boiling aromatic hydrocarbons. Toobtain suspensions or emulsions in water, wetting agents may also beadded.

Flowables are prepared by mixing an active compound with one or moredispersing agents and/or solid additives, and a liquid (which may bewater or an organic solvent) in which the active compound is relativelyinsoluble, and grinding the mixture.

Both liquid and solid compositions may be in microcapsule orencapsulated form, to permit release of the enclosed active compound ata controlled rate over a period of time. Liquid compositions of thistype contain encapsulated droplets of approximately 1-50 microns indiameter, including the active compound and optionally a solvent. Theencapsulating material is an inert porous membrane of a polymericmaterial.

Solid encapsulated compositions generally take the form of granules, inwhich the liquid containing the active component is trapped in the poresof the granular support by a porous polymeric membrane through which theactive ingredient may migrate at a controlled rate, or which membranebreaks down at a controlled rate to permit escape of the activeingredient.

Typical encapsulating materials include natural and synthetic rubbers,cellulosic materials, sytrene-butadiene copolymers, polyacrylonitriles,polyacrylates, polyamides, polyisocyanates, polyurethanes, mixedcopolymers of the foregoing and starch xanthates.

It is possible to use highly concentrated liquid compositions containingup to about 95% by weight of the active compound, or even the 100%active compound alone, when applying the compound in the form of afinely divided liquid by use of various atomizing equipment, for exampleby airplane spraying techniques. For other purposes, however, thevarious types of compositions which can be utilized for these compoundswill contain varying amounts of the compound according to the type ofcomposition and the intended use.

In general, insecticidal compositions may contain from 5 to 95% of theactive compound, more preferably from 10 to 85%. Some typicalcompositions will contain an active compound as follows: wettablepowders: 25 to 80% active compound; oil suspensions, emulsions,solutions, flowables, and emulsifiable concentrates: 5 to 85% activecompound; aqueous suspensions: 20 to 50% active compound; dusts andpowders: 5 to 20% active compound; granules and pellets: 5 to 20% activecompound.

In addition to the active compound and the various agents utilized inpreparing compositions and formulations mentioned, such compositions mayalso contain one or more other active compounds of the type mentionedherein as well as other active pesticidal agents, such as herbicides,fungicides, insecticides, acaricides, nematocides, bactericides, andplant growth regulators. The particular pesticide included in themixture will depend upon its intended utility and the type ofcomplementary action required. Examples of suitable insecticides includethe following:

(a) natural pyrethrins or pyrethroids such as permethrin, esfenvalerate,deltamethrin, cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin,tefluthrin, empenthrin, ethofenprox, natural pyrethrins, tetramethrin,bioalletrrin, fenfluthrin, prallethrin,5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, andpentafluorobenzyl(cis)-3-[2-fluoro-2-(methoxycarbonyl)ethenyl]-2,2-dimethylcyclopropanecarboxylate.

(b) organophosphates such as profenofos, sulprofos, phosmet, cichlorvos,methyl parathion, axinphos-methyl-dimeton-s-methyl, heptenophos,thiometon, fenamiphos, monocrotophos, profenophos, triazophos,methamidophos, diemthoate, phosphamidon, malation, chlorpyrifos,phosalone, fensulfothion, fonofos, phorate, phoxim, pyrimiphos-methyl,fenitrothion and diazinon;

(c) carbamates (including aryl carbamates) such as pirimicarb,cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan,bendiocarb, fenobucarb, propoxur and oxamyl;

(d) benzoyl ureas such as triflumuron, chlorofluazuron;

(e) organic tin compounds such as cyhextin, fenbutatin oxide, andazocyclotin;

(f) macrolides such as avermectins or milbemycins, for example such asabamectin, avermectin, and milbemycin;

(g) hormones and synthetic mimics thereof such as juvenile hormone,juvabione, ecdysones, methoprene and hydroprene;

(h) pheromones; and

(i) organochlorine compounds such as benzene hexachloride, DDT,chlordane or dieldrin.

In addition to the major chemical classes of insecticide listed above,other insecticides having particular targets may be employed in themixture if appropriate for the intended utility of the mixture. Forinstance selective insecticides for particular crops, for examplestemborer specific insecticides for use in rice such as cartap orbuprofesin, can be employed. Alternatively, insecticides specific forparticular insect species/stages, for example ovolarvicides such asclofentezine, amitraz, chlordimeform flubenzimine, hexythiazox andtetradifon, motilicides such as dicofol or propargite, adulticides suchas bromopropylate, chlorobenzilate, or insect growth regulators such ashydramethylon, cyromazine, methoprene, chlorofluazuron and diflubenzuronmay also be included in the compositions. Such compositions may alsocontain soil disinfectants or fumigants and may further containfertilizers, thus making it possible to provide multi-purposecompositions containing one or more of the active compounds describedherein as well as, optionally, other pesticides and also fertilizers,all intended and formulated for use at the same locus.

Control of insect pests is accomplished by applying a compositioncontaining an insecticidally effective amount of an active compound asdescribed herein to the insect, to a locus at which insecticidal controlis desired, or to food sources (including seeds) on which the insectsfeed. For use in the last mentioned manner it is preferable to utilize acompound which is not volatile. Thus, control may be achieved by directapplication of the active compounds to the insects and indirectly byapplication of the compounds to a locus to be protected (such as croplands, grass ranges and forests), to a source of food for insects or toother insect habitats (for example, breeding or swarming areas). Therates of application of the active compound, and the concentrationapplied, will vary according to whether the compound or composition isbeing directly applied to the insect or indirectly, to a locus, food orhabitat. In the latter case the rate of the application, depending onthe nature of the insect or insects to be controlled, and the planeenvironment, will generally vary from about 0.01 to about 100 pounds peracre (about 0.011 at about 111 kg/ha).

It should be noted that the active compound need not be insecticidallyactive per se to effect insect control. The purposes of this inventionare fully served if such compounds are rendered active by externalinfluences, such as light or heat, or by some physiological action whichoccurs when the compound is ingested into the body of the insect.

Compounds of this invention could be used to control a variety ofinsects such as:

Myzus persicae (aphid)

Aphis gossypii (aphid)

Aphis fabae (aphid)

Megoura viceae (aphid)

Aedes aegypti (mosquito)

Anopheles spp. (mosquitos)

Culex spp. (mosquitos)

Dysdercus fasciatus (capsid)

Musca domestica (housefly)

Pieris brassicae (white butterfly)

Plutella maculipennis (diamond back moth)

Phaedon cochlaeriae (mustard beetle)

Aonidiella spp. (scale insects)

Trialeuroides spp. (white flies)

Bemisia tabaci (white fly)

Blattella germanica (cockroach)

Periplaneta americana (cockroach)

Blatta orientalis (cockroach)

Spodoptera littoralis (cotton leafworm)

Heliothios virescens (tobacco budworm)

Chortiocetes terminifera (locust)

Diabrotica spp. (rootworms)

Agrotis spp. (cutworms)

Chilo suppressalis (stem borer)

Chile partellus (maize stem borer)

Nilaparvata lugens (planthopper)

Nephottex virescens (leafhopper)

Nephtoettix cincticeps (leafhopper)

Panonychus ulmi (European rod mite)

Panonychus citri (citrus red mite)

Tetranychys urticae (two-spotted spider mite)

Tetranychus cinnabaminus (carmine spider mite)

Phyllcoptruta oleivora (citrus rust mite)

Polyphagotarsonemus latus (broad mite)

Brevipalpus spp. (mites)

Compositions containing one or more of the active compounds described,in an insecticidally effective amount, may be applied to the plant,locus or insect habitat in any conventional manner.

When used in connection with crop or other plant protection, applicationmay be made in a preventive (i.e. before infestation) or eradicativemanner (i.e., after infestation). Thus, powders and various liquidcompositions containing the active compound can be applied by the use ofpower dusters, boom and hand sprayers and spray dusters, or applied fromairplanes as dusts or sprays. When applied in the latter method they maybe effective in very low dosages.

Compositions including active compounds may also be applied by additionto irrigation waters supplied to the field to be treated. This method ofapplication permits penetration of the compounds into the soil as thewater is absorbed therein.

Compositions including active compounds may additionally be used toprotect plant seeds from being attacked by soil-borne insect pests afterplanting and during germination, by applying the composition to theseeds as a seed dressing. This is performed generally by mixing theseeds with an active composition in either liquid or solid form(preferably liquid) in a suitable mixing apparatus. Liquid compositionsfor this purpose may contain an adhesive or sticking agent, such asmethyl cellulose, ethyl cellulose, etc., to assist the composition inadhering to the seed. If a solid composition is utilized for thispurpose, an adhesive agent may be sprayed on the seeds during or aftermixing.

For use as a soil insecticide, the active compound, or compositionscontaining it, may be mixed with the soil in any conventional manner,before, during or after planting of the plant seeds. Liquid compositionsmay be applied by spraying onto the surface or by incorporation inirrigation or sprayed water. Solid or liquid compositions containing anactive compound may be incorporated into the soil prior to or duringplanting by discing, plowing or other mixing operations, or afterplanting as a side dressing, in order to locate the active ingredientbelow the surface of the soil so as to be most effective in controllingundesirable larvae.

Some examples of compositions containing the active compounds of thisinvention are:

    ______________________________________                                        Component           Weight %                                                  ______________________________________                                        Composition A: Granular Solid                                                 Active compound     10                                                        attapulgite clay granules                                                                         85                                                        triethylene glycol   5                                                        Total                100%                                                     Composition B: Wettable Powder                                                Active compound     80                                                        wetting agent (sodium dialkyl-                                                                     1                                                        naphthalene sulfonate)                                                        dispersing agent (sodium                                                                           4                                                        lignosulfonate)                                                               diluent (aluminum magnesium                                                                       15                                                        silicate)                                                                     Total                100%                                                     Composition C: Dilute Solution                                                Active compound     5                                                         solvent (xylene)    95                                                        Total               100%                                                      Composition D: Emulsifiable Concentrate                                       Active compound     50                                                        Emulsifier (blend of metal                                                                        10                                                        sulfonates and polyoxy-                                                       ethylene ethers)                                                              solvent (xylene)    40                                                        Total                100%                                                     Composition E: Concentrated Solution                                          Active compound     90                                                        solvent (xylene)    10                                                        Total                100%                                                     ______________________________________                                    

What is claimed is:
 1. A compound having the formula ##STR90## whereinR₁ is quinolyl or isoquinolyl;R₂ is methyl, ethyl, n-propyl, C₃ -C₇branched alkyl, C₃ -C₄ cycloalkyl, C₂ -C₆ alkenyl, C₂ -C₆ haloalkenyl,C₁ -C₆ haloalkyl, C₂ -C₆ alkoxyalkyl or cyclopropyl substituted by up tofour methyl groups or up to two halogens; X is oxygen, sulfur or --NH--;and when X is oxygen, then R₃ is:(a) ##STR91## in which m is 0 or 1; A,B and C are each carbon or nitrogen, provided that A, B and C are notall nitrogen and if two of A, B and C are nitrogen, than A and C arenitrogen; R₄ is hydrogen, monohalo or dihalo; R₆ is hydrogen, methyl,fluoro or ethynyl; and R₇ is(i) ##STR92## in which D and E are eachcarbon or nitrogen provided that both D and E are not nitrogen, andfurther provided that if either A, B or C is nitrogen, then D and E areboth carbon; and R₅ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,trifluoromethyl, cyano, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, or mono-or polyhalo;(ii) ##STR93## in which R₈ is hydrogen or halogen; or (iii)--O--CH₂ --CH═CH₂ (b) ##STR94## in which (i) R₉ is 4-fluoro,4-methoxymethyl, or 4-propargyl, and R₁₀ is fluoro or(ii) R₉ is 3- or4-allyl, 3- or 4-propargyl, or 3- or 4-(mono- or dihalo)allyl, and R₁₀is hydrogen or fluoro; (c) ##STR95## (d) 4-phenoxy-2-butyn-2-yl; (e)4-(benzyloxy)benzyl; (f) 4-(4-fluorobenzyloxy)benzyl; or (g) ##STR96##and if X is sulfur or --NH--, then R₃ is (h) ##STR97## in which n is 0or 1; F and G are independently nitrogen or carbon, provided that F andG are not both nitrogen; R₁₁ is hydrogen or halo; R₁₂ is hydrogen, mono-or di-halo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethyl, cyano, C₁ -C₄alkylthio, C₁ -C₄ alkylsulfonyl; and R₁₃ is hydrogen or methyl; (i)pentafluorobenzyl; or (j) 2-methyl-3-phenylbenzyl.
 2. A compoundaccording to claim 1 in which R₃ has the formula ##STR98## in which A isnitrogen or carbon and R₄ and R₅ are each independently hydrogen orhalogen.
 3. A compound according to claim 2 in which A is carbon, and R₄and R₅ are both hydrogen.
 4. A compound according to claim 2 in which Ais carbon, R₄ is hydrogen and R₅ is halogen.
 5. A compound according toclaim 2 in which A is carbon, R₄ is halogen and R₅ is hydrogen.
 6. Acompound according to claim 2 in which A is carbon and R₄ and R₅ areboth halogen.
 7. A compound according to claim 6 in which R₄ is fluoroand R₅ is chloro.
 8. A compound according to claim 1 wherein X isoxygen.
 9. A compound according to claim 8 wherein R₃ is3-phenoxy-benzyl.
 10. A compound according to claim 11 wherein R₂ isisopropyl.
 11. The compound according to claim 10 in which R₁ is6-quinolyl.
 12. The compound according to claim 10 wherein R₁ is3-quinolyl.
 13. A compound according to claim 9 wherein R₂ iscyclopropyl.
 14. A compound according to claim 8 wherein R₃ is3-(4-fluorophenoxy)benzyl.
 15. A compound according to claim 1 whereinR₂ is isopropenyl and X is oxygen.
 16. A method for controlling insectscomprising applying to an insect, the locus of an insect or a locus atwhich insecticidal control is desired, an insecticidally effectiveamount of a compound according to claim
 1. 17. An insecticidalcomposition comprising (a) an insecticidally effective amount of acompound according to claim 1; and (b) an insecticidally suitablediluent or carrier.